Chemical compositions



United States Patent 2,925,429 CHEMICAL COMPOSITIONS Willard H.Kirkpatrick, Sugar Land, and Alice Walker, Houston, Tex., assignors toVisco Products Company,- Houston, Tex., a corporation of Delaware NoDrawing. Original application September 30, 1950, Serial No. 187,824.Divided and this application July 12, 1954, Serial No. 442,897

14 Claims. (Cl. 260404.8)

This invention relates to new and improved chemical compositions andmore particularly to new and improved chemical compositions containingboth hydrophobe and hydrophile groups.

An object of the invention is to provide new and useful compositionswhich have a hydrophile-hydrophobe balance which makes them especiallyuseful as demulsifiers for water-in-oil petroleum emulsions and 'forother uses where such a hydrophile-hydrophobe balance is necessary ordesirable.

The compositions of. the present invention are reaction products ofcastor oil, an organic dicarboxy acid and a polyoxyalkylene compound,preferably having a molecular weight of at least 1700, which may beeither a glycol or a monoether of a glycol and in which the oxyalkylenegroups consist essentially of oxyethylene and oxypropylene groups (e.g.,oxy-1,2-propylene) wherein the weight ratio of oxyethylene tooxypropylene is at least 1:4 and does not exceed 4:1.

The order of the reactions does not appear to be important but is isusually preferable to react the castor oil with the dicarboxy acid firstand then to react the resultant product with the polyoxyalkylenecompound. The reactions are carried out under conditions facilitatingthe elimination of an aqueous distillate.

The proportions of the reactants may vary but, in general, the molarratio of the dicarboxy acid to castor oil should be at least 1:3 and themolar ratio of the polyoxyalkylene compound to castor oil likewiseshould be at least 1:3.

The temperatures of reaction will normally be within the range of 150 C.to 300 C.

The reaction is preferably carried out sufficiently long to eliminatethe major proportion of the water formed at the reaction temperaturesbut short of the formation of a solid gel.

The reaction products have a relatively high molecular weight. For thebest results in breaking petroleum emulsions polyoxyalkylene compoundshaving a molecular weight within the range from about 1700 to about 7500have been employed in preparing the desired products.

It has been discovered that these compositions have unusual andunexpected properties for resolving waterin-oil emulsions into theircomponent parts. One possible theory which may be postulated for thestriking effectiveness of these compositions in resolving petroleumemulsions is hydrophobe-hydrophile balance which has not been securedheretofore with compositions well known in this art.

Since as indicated above it is possible to prepare the compositions ofthis invention by various routes and from a number of different classesof starting materials the invention should not be limited by thefollowing examples which are merely intended to illustrate somesatisfactory procedures for preparing a few of the materials suitablefor employment within the scope of the present invention.

EXAMPLE I In a suitable reaction vessel there was introduced 4480 acid.The temperature was raised with agitation until 2,925,429 Patented Feb.16, 1960 an aqueous distillate began to form at a temperature of about150 C. The heating was continued until 166' parts of an aqueousdistillate had been secured at a maximum temperature of about 170 C.-The reaction mass was then cooled to 145 C. and condensed at thistemperature for 4 hours. Approximately 5400 parts of a composition knownin the trade as Ucon SO-HB-660 and about 1080parts of a suitablehydrocarbon fraction such as S0,, vextract were added to the aboveintermediate. Ucon 50-HB 660 is the monobutyl ether of a hetericpolyalkylene glycol, the polyoxyalkylene chain of which containsethylene oxide and propylene oxide in a 1:1 ratio, the molecular weightof the monoetherbeing approximately 1700. After the addition of thesematerials the temperature of the reaction mass is gradually increaseduntil a second aqueous distillate began to form. The heating,wascontinued until atotal of about 42 parts of aqueous distillate wassecured. The formation of the distillate began at approximately 185 C.and the required amount was secured at a maximum temperature of about 7230 C. After coolingto approximately 140 C. 2880 EXAMPLE II V In asuitable reaction vessel 930 parts of castor oil and201'parts oftechnical diglycolic acid were heated until36 parts of an aqueousdistillate had been secured. After the aqueous distillate was securedthe reaction mass was permitted to condense an additional 2 hours at C.To 220 parts of this intermediate there was added 170 parts of Ucon50-HB-660' and 50 parts of a suitable hydrocarbon fraction such as S0extract. The mixture was then heated with agitation and at approximately218 C. an aqueous distillate began to form and heating was continued.until approximately 2 parts of aqueous distillate was secured at amaximum temperature of 253 C. The mass was cooled to C. and 400 parts ofS0 extract added with agitation to yield the finished product.

EXAMPLE III In a suitable reaction vessel provided with means ofagitation, heating and removal of aqueous distillate with simultaneousreturn of azeotropic distillate to the reaction mass there was added 630parts of castor oil and 148 parts of phthalic anhydride. These materialswere heated and condensed for 7 hours'at a temperature of 140 to 155 C.To 250 parts of this intermediate there was added 250 parts of Ucon50-HB-660 and 50 parts of S0 extract. The reaction mass was heated to220 C. An aqueous distillate began to form and heating was continued for2. hours at a maximum temperature of 258 C. Approximately '3 parts ofaqueous distillate was secured under these conditions. The reaction masswas cooled to 140iC.'. and about 660 parts of S0 extract was added withstirring to yield the finished product. a 1

- EXAMPLE IV Under similar conditions to those described in Example III,930 parts of castor'oil and 268 parts of technical diglycolic acid wereheated with agitation until a total of 36 parts of aqueous distillatewas secured. This reaction began at 159" C, and was completeafter-approximately 2 hours at a maximum temperature of 172 C. The heatwas then reduced to C. and the mass condensed at that temperature for 4hours. 'To 116 parts of the above intermediate ,there' were added 500parts of Ucon 50-HB-5100 and 100 'parts of S0 extract. Ucon.50-HB5100 isa monobutyl ether of .a heteric polyoxyalkylene glycol in which ethyleneoxideand propylene oxide are present in a ratio of 1:1 and the molecularweight is approximately 5000. The reaction mixture was heated withagitation and at 197 C. an aqueous distillate began to form. and heatingwas continued until a total of 2.2 parts of aqueous distillate had beensecured at a maximum temperature of 245 C. The reaction mass was cooledto approximately 140 C. and 1325 parts of S extract was added withagitation to yield the finished product.

EXAMPLE V The procedure of Example IV was repeated with the exceptionthat 19 parts of Ucon 75-H-l35 was used in place of the Ucon 50-HB-5100.Ucon 75-H-l35 is a heteric polyoxyalkylene glycol in which the ethyleneoxide to propylene oxide ratio is 3:1 and the molecular weight isapproximately 325. Also, in this example only 400 parts of S0 extractwas used in the final step to yield the finished product.

EXAMPLE VI Under similar conditions described in Example III, 315 partsof castor oil and 67 parts of technical diglycolic acid were heated tosecure 9.2 parts of an aqueous distillate. This reaction requiredapproximately 80 minutes at a temperature of 162 to 180 C. The heat wasthen lowered to 150 C. and condensation permitted to occur at thistemperature for an additional 5 hours. To 100 parts of this intermediatethere was added 130 parts of Ucon 75-H-1400 and 50 parts of S0 extract.Ucon 75-H-1400 is a heteric polyoxyalkylene glycol in which the ethyleneoxide to propylene oxide ratio is 3:1 and the molecular weight isapproximately 2200. These reactants were heated over the range from 197C. to 240 C. during which 1.1 parts of aqueous distillate was secured.The reaction mass was cooled to approximately 140 C. and 325 parts of S0extract added with stirring to yield the finished product.

EXAMPLE VII Under similar conditions to those described in Example III,110 parts of castor oil, diglycolic acid intermediate as prepared inaccordance with Example II, 50 parts of Ucon 75-H-135 and 20 parts of S0extract were mixed with heating. The temperature was held at 150 C. for2 hours and then gradually raised until an aqueous distillate began toform at 182 C. Heating was continued for 2 hours and a maximumtemperature of 276 C. During this reaction time 2.7 parts of an aqueousdistillate was secured. The reaction mass was cooled to 140 C. and 190parts of S0 extract added with stirring to yield the finished product.

EXAMPLE VIII Under conditions similar to those described in Example III,189 parts of castor oil and 40 parts of technical diglycolic acid wereheated to lose 7.2 parts of an aqueous distillate. This reactionrequired approximately 3.5 hours at an initial temperature of 140 C. anda maximum temperature of 228 C. To this intermediate there was added 370parts of Ucon 25-HDG and 50 parts of S0 extract. Ucon 25- HDG is aheteric polyoxyalkylene glycol having an ethylene oxide to propyleneoxide ratio of 1:3 and a molecular weight of about 3000. These reactantswere heated for approximately 0.5 hours between 220 C. and 250 C. Duringthis interval 1.9 parts of aqueous distillate were secured. The reactionmass was cooled to approximately 140 C. and 300 parts of SO: extractwere added to yield the finished product.

In the foregoing examples, the quantities are given in parts by weight.Examples I, II, III, IV, VI and VIII, the average molecular weight ofthe product attributable to the polyoxyalkylene compound is at least1700. Within the limits previously defined, any of the diols describedin U.S. Patent 2,425,845 and any of the monoethers described in U.S.Patent 2,448,664 may be sub stituted for the respective diols andmonoethers in the foregoing examples.

By way of illustrating the remarkable effectiveness of the productscontemplated by this invention, the method of testing their efiiciencyin bottle tests will be described and exemplary data given, and thiswill be followed by the results of a full scale plant test.

Field bottle test I State of Arkansas. Oil field Smart. Oil company R.H. Crow Drilling. Lease Taylor. Well B-l. Percent emulsion in fluid fromthe well 65. Percent water in the fluid from the well 0 Percent waterobtained by complete demulsification 54. Temperature of test 150 F.Manual agitation 50.hot shakes,

200 cold shakes. Treating ratio 1/5,000.

One hundred cc. samples of the emulsion were taken and placed inconventional field test bottles. Various treating chemicals were addedto the bottles at a ratio of 1 part chemical to 5,000 parts emulsionfluid. After the test chemical was added the samples which were placedin the test bottles were shaken 200 times at atmospheric temperature andsubsequently agitated an additional 50 times at a treating temperatureof F. After shaking in each instance the water-drop was determined andrecorded, that is to say, the amount of water which separated from theemulsion. The color of the oil was also observed and recorded at thesame time. After agitation at elevated temperature, the samples weremaintained at 150 F. for a total of 60 minutes to permit settling andstratification of the water.

The emulsion sample was secured just after the oil came from the welland every effort was made to maintain conditions comparable to thosepresent in a full scale plant treatment. After agitation the sampleswere allowed to settle and were tested for water-drop at predeterminedperiods of time and recorded on suitable test sheets. The test showedthat the composition as prepared in accordance with instructions ofExample II released 27 parts of water after cold agitation. After thebottles had reached treating temperature of 150 F. the composition ofExample II had dropped 50 parts of water and after standing 60 minutesat treating temperature the water-drop increased slightly. The color ofthe oil using Example II composition was excellent. The treated oilcontained no residual emulsion whereas the chemical being usedcommercially in the plant system showed 1.2 parts of emulsion remainingwhich had not been resolved.

Field bottle test ll State of Texas. Oil field Forsan. Oil company a-Continental. Lease Eason. Well No.1. Percent emulsion in fluid from thewell 55. Percent water in the fluid from the well 10. Percent waterobtained by complete demulsification 43. Temperature of testAtmospheric. Manual agitation 200 cold shakes. Treating ratio 1/33,300.

, ing 10 minutes. After 20 minutes standing approximately 25 parts ofwater had separated. Upon additional standmg substantially all of therecoverable water had separated. The treated oil with Example I and IIcomposiiw tions met pipeline specifications and could be successfullyused in commercial scale operations.

Field bottle test III State of Arkansas. Oil field Shuler. Oil companyLion. Lease C. Wells No. 16, 17. Percent emulsion in fluid from the well60. Percent water in the fluid from the Well 4. Percent water obtainedby complete demulsification 39. Temperature of test 140 F. Manualagitation 200 cold shakes, 100 hot shakes. Treating ratio 1/10,000.

Using the procedure similar to that described in Field bottle test I,tests were made using compositions as prepared in Examples I and II.Both gave excellent color to the resolved oil indicating substantialbreaking of the emulsion. After 10 minutes at treating temperature of140 F. 20 parts of water had stratified and upon standing an additional20 minutes all of the water had stratified and the treated oil showedtrace or less emulsion and water present. Under identical conditions,the chemical being used commercially dropped only 5 parts'of'water afterminutes standing and 35 parts after an'additional 20 minutes standing.The oil layer with this chemical contained 16% emulsion and 1.2% water.

Field plant scale test This test was made by actually treating the oilcoming from the well described in Field bottle test III. A Nationalheater treater was being used with a chemical proportioning pump to addthe chemical treating reagent.

The treating agent employed was prepared in accordance with thedirections of Example II. The plant test Was started at 8:00 am. and wasobserved continuously until 1:00 pm. of the following day. During thisplant test an average of 26 pints of chemical was used during a 24 hourperiod. In this 24 hour period 1200 barrels of substantially dry oilwere produced. During this test the treated oil met pipelinespecifications and averaged less than 2% emulsion and water.Observations made during this plant test indicated that an excess amountof chemical had been used and subsequent plant tests demonstarted thatthis oil could be treated using as little as 12 pints of chemical per 24hours which is a treating ratio of 800 barrels of net oil per gallon ofchemical.

The treating ratio with the commercial chemical used previously was 1gallon of chemical to 300 barrels of net oil.

is abyproduct from the Edeleanu process of refining ps troleum in which.the undesirable fractions are removed by extraction with liquid sulfurdioxide. After removal of the sulfur dioxide a mixture ofhydrocarbons,'substantially aromatic in character, remains which isdesignated in the trade as S0 extract. Examples of other suitablehydrocarbonvehicles-are Gray Tower polymers, toluene, xylene, gas oil,diesel fuel, Bunker fuel and coal tar solvents. The above cited examplesof solvents are adaptable to azeotropic distillation as would also beany other, solvent which is immiscible with water, miscible with thereacting mass and has a boiling point or boiling range in excess ofthe-boiling point of water.

' The products prepared in accordance with'the invention are very useful'in breaking petroleum emulsions, especially those in which the oil isparafiinic'or parafiinicnaphthenic, and .have been successfully used inbreaking water-in-oil petroleum emulsions in the Mid-Continent oilfields, including Oklahoma, Illinois, Kansas, the Gulf coast, Louisiana,Southwest Texas and California.

tion Serial No. 187,824, filed September 30, 1950, now

abandoned.

,The invention is hereby claimed as follows:-

1. The product of the reaction at ISO-300 C. of castor oil, an organicdicarboxy acid and a polyoxyalkylene compound having an averagemolecular weight between about 1700 and 7500 from'the group consistingof glycols and monoethers of glycols in which the oxyalkylene groupsconsist essentially of oxyethylene and oxypropylene groups and theweight ratio of oxyethylene to oxypropylene is at least 1:4 and notgreater than 4: 1, the molar ratio of dicarboxy acid to castor oil beingat least 1:3 and the molar ratio of the polyoxyalkylene compound tocastor'oil being at least 1:3.

2. The product of'the reaction at -300" C. of castor oil, an organicdicarboxy acid and a polyoxyalkylene glycol having an average molecularweight between about 1700 and 7500 in which the oxyalkylene groupsconsist essentially of oxyethylene and oxypropylene groups and theweight ratio of oxyethylene to oxypropylene is at least 1:4 and-notgreater than 4:1, the productot .reaction being formed by firstreactingthe dicarboxy acid and the castor oil at a molar ratio of atleast 1:3, respectively, at 150-300 C. with the elimination of the waterof reaction and thereafter reacting the resulting product tween about1700 and 7500 in which the oxyalkylene groups consist essentially ofoxyethylene and oxypropylene The demulsifying compositions arepreferably employed in the proportion of 1 part of reagent to from 2000to 50,000 parts of emulsion either by adding the concentrated productdirect to the emulsion or after diluting with a suitable vehicle in thecustomary manner.

The suitable hydrocarbon vehicle referred to in the examples is sulfurdioxide (S0 extract. This-materia17 5 groups and the weight ratio ofoxyethylene to oxypropylene is at least 1:4 and notgreater than 4:1, the

product ofreaction being formed by first reacting the dicarboxy acid andthe castor oil at a molar ratio of at least 1:3, respectively, atISO-300 C. with the elimination of the Water of reaction and thereafterreacting the resulting product with said polyoxyalkylene compoundat150-300 C. with the elimination of the water of reac-' g-lycolic acidand :a polyoxyalkylen'e compound having an average molecular weightbetween about 1700 and 7500 from the group consisting of glycols andmonoethers of glycols in which the oxyalkylene groups consistessentially of oxyethylene and oxypropylene groups and the weight ratioof oxyethylene to oxypropylene is at least 1:4 and not greater than 4:1,the product of reaction being formed by first reacting the diglycolicacid and the castor oil at a molar ratio of at least 1:3, respectively,at 150300 C. with the elimination of the water of reaction andthereafter reacting the resulting product with said polyoxyalkylenecompound at ISO-300 C. with the elimination of the water of reaction ata molar ratio of the polyoxya lkylene compound to the :castor oil in thecastor oil-diglycolic acid reaction product of at least 1:3.respectively.

5. The product of the reaction at 150-300 C. with the elimination of thewater of reaction of castor oil, vdiglycolic acid and a polyoxyalkyleneglycol having an average molecular weight between about 1700 and 7500 inwhich the oxyalkylene groups consist essentially of oxyethylene andoxypropylene. groups and the weight ratio of oxyethylene to oxypropyleneis at least 1:4 and not greater than 4: 1, the product of reaction beingformed by first reacting the diglycolic acid and the castor oil at amolar ratio of at least 1:3, respectively, at l50300 C. with theelimination of the water of reaction and thereafter reacting theresulting product with said polyoxyalkylene glycol at ISO-300 C. withthe elimination of the water 'of reaction at a molar ratio ofpolyoxyalkylene glycol to the castor oil in the castor oil-diglycolicacid reaction product of at least 1:3, respectively.

6. The product of the reaction at ISO-300 C. with the elimination of thewater of reaction of castor oil, di glycolic acid and a polyoxyalkyleneglycol monoether having an average molecular weight between about 1700and 7500 in which the oxyalkylene groups consist essentially ofoxyethylene and cxypropylene groups and the weight ratio of oxyethyleneto oxypropylene is at least 1:4 and not greater than 4:1, the product ofreaction being formed by first reacting the diglycolic acid and thecastor oil at a molar ratio of at least 1:3, respectively, at ISO-300 C.with the elimination of the water of reaction and thereafter reactingthe resulting product with said polyoxyalkylene glycol monoether at150-300 C. with the elimination of the water of reaction at a molarratio of the polyoxyalkylene glycol monoether to the castor oil in thecastor oil-diglycolic acid reaction product of at least 1:3,respectively.

7. The .product of the=condensation with the elimination of water ofcastor oil, an organic dicarboxy acid and a polyoxyalkylene compoundhaving an average molecular weight between about 1700 and 7500 from thegroup consisting of glycols and monoethers of glycols in which theoxyalkylenegroups consist essentially of oxyethylene and oxypropylenegroups and the weight ratio of oxyethylene to oxypropylene is within therange of 1:4 to 4:1, the molar ratio of the dicarboxy acid to castor oilbeing at least 1:3 and the molar ratio of the polyoxyalkylene compoundto castor oil being at least 1:3.

8. The product of the condensation with the elimination of waterof-castor oil, an organic dicarboxy acid and a polyoxyalkylene compoundfrom the group consisting of glycols and monoethers of glycols in whichthe oxyalkylene groups consist essentially of oxyethylene andoxypropylene groups and the weight ratio of oxyethylene to oxypropyleneis within the range of 1:4 to 4:1, the average molecular weight .of saidproduct attributable to said polyoxyalkylrene compound being at least1700, 'the' mola'r ratio of the dic'arboxy acid to 'castor oil being "atleast 1:3 and the molar ratio of the polyoxyalkylene compound to castoroilbe'ing at least 1:3.

9. The product of the condensation with the elimination of water ofcastor oil, an organic dicarboxy acidand a polyoxyalkylene compoundtrcmthe group consisting of least 1:3 and the molar ratio of thepolyoxyalkylene 5 compound to castor oil being at least 1:3.

10. The product of the condensation with the elimina- I tion of water ofcastor oil, an organic dicarboxy acid and a monoether of apolyoxyalkylene glycol in which the oxyalkylene groups consist essentialof oxyethylene and oxy-1,2-propylene groups and the weight ratio ofoxyethylene to oxy--1,2-propylene is within the range of 1:4 to 4:1, theaverage molecular weight of said product attributable "to saidpolyoxyalkylene glycol monoether being within the range from 1700 to7500, the molar ratio of the dicarboxy acid to castor oil being at least1:3 and the molar ratio of the polyoxyalkylene compound to castor oilbeing at least 1:3.

11. The product of the condensation with the elimination of water ofcastor oil, an organic dicarboxy acid and a polyoxyalkylene glycol inwhich the ox-yalkylene groups consist essentially of oxyethylene andoxy-1,2-propylene groups and the weight ratio of 'oxyethylene tooxy-1,2- propylene is Within the range of 1:4 to 4:1, the averagemolecular weight of said product attributable to said polyoxyalkyl'eneglycol being within the range from 1700 to 7500, the molar ratio of thedicarboxy acid to castor oil being at least 1:3 and the molar ratio ofthe polyoxyalkylene glycol to castor oil being at least 1:3.

12. The ;.product of the condensation with the elimination of water ofcastor oil, diglycolic acid and a polyoxyalkylene compound from thegroup consisting of glycols and .monoethers of glycols in which theoxyalkylene groups consist essentially of oxyet'hylene and oxypropylenegroups and the weight ratio of oxyethylene to oxypro- .pylene is withinthe range of 1:4 to 4:1, the average molecular weight of saidpolyoxyalkylene compound being within the range from 1700 to 7500, themolar ratio of the diglycolic acid to castor oil being at least 1:3 andthe molar ratio of the polyoxyalkylene compound to castor oil being atleast 1:3.

13. The product of the condensation with the elimination of water ofcastor oil, diglycolic acid and a monoether of a polyoxyalkylene glycolin which the oxyalkylene groups consist essentially of oxyethylene andoxy-1,2-propylene groups and the weight ratio .of oxyethylene tooxy-1,2-propylene is within the range of 1:4 to 4:1, the averagemolecular weight vof said product attributable to said .polyox-yalkyleneglycol monoether being within the range from 1700 to '7500, the molarratio of the diglycolic acid to castor oil being at least 1:3 and themolar ratio of the .polyoxyalkylene glycol to castor oil being at least1:3:

14. The product of the condensation with the elimination of water ofcastor oil, diglycolic acid and a polyoxyalkylene glycol in which theoxyalkylene groups consist essentially of .oxycthylene andoXy-1,2-propylene groups and the weight ratio of oxyethylene to oXy-1,2-ipropylene is within the range of 1:4 to 4:1, the average molecularweight of said product attributable to said polyoxyalkylene glycol beingwithin the range from 1700 to 7500, the molar ratio of the diglycolicacid to castor oil being at least 1:3 and the molar ratio of thepolyoxyalkylene glycol tocastor oil being at least 1:3.

References Cited in the file of this patent UNITED STATES PATENTS2,295,163 De Groote et al. Sept. 8, 1942 2,505,824 De Groote et al. May2, 1950 2,576,285 De Groote'et al. Nov. 27, 1951 2,677,700 Jackson etal. May 4, 1954 2-,695;909 Smith Nov. 30, 1954

1. THE PRODUCT OF THE REACTION OF 150-300*C. OF CASTOR OIL, AN ORGANICDICARBOXY ACID AND A POLYOXYALKYLENE COMPOUND HAVING AN AVERAGEMOLECULAR WEIGHT BETWEEN ABOUT 1700 AND 7500 FROM THE GROUP CONSISTINGOF GLYCOLS AND MONOETHERS OF GLYCOLS IN WHICH THE OXYALKYLENE GROUPSCONSIST ESSENTIALLY OF OXYETHYLENE AND OXYPROPYLENE GROUPS AND THEWEIGHT RATIO OF OXYETHYLENE TO OXYPROPYLENE IS AT LEAST 1:4 AND NOTGREATER THAN 4:1, THE MOLAR RATIO OF DICARBOXY ACID TO CASTOR OIL BEINGAT LEAST 1:3 AND THE MOLAR RATIO OF THE POLYOXYALKLENE COMPOUND TOCASTOR OIL BEING AT LEAST 1:3.